Amine derivatives of chloromethyl dihydrosafrol



.. a .HermanWacha Brooklyn, Y ass ignor to S.

Patented Sept. 12 1950 ..;.;-,2,521 ,s11 7 AMINE DERIVATIVES oFfdiiiioltpM il Y AFEQH," 1

industrial,,ohemicalslrna, New York, t n' f Delaware I v v 1 r Y mbracing: Application April 27,21949, sale .No. 90,041; In BrazilMarch 26, 1947 cl im (as; fl)

tion of various products falling Withll'l the scope ofithls invention. v that '.s: :"-1 r "eflEz" The cyclohexylamine" rescue maua was prepared as follows: 52.5 grams (0.53 mole) of cyclohexylamine was dissolved in 23 grams ,of atoms in each alkyl radical, cyclohexylamine, benzene. 53 grams (0.265 o e of l r y morpholine and piperidine, with a splitting ofi d ydr a ol was added under cooli t e m f t appropriate halggen id l0 ture was allowed to stand for two hours, and chloromethyl and bromomethyl dlhydrosafrol was thereafter refluxed on a steam bath. Water are materials having the generic formula. was then added, the oil was separated, benzene distilled ofi, and steam was passed through the remainder to remove excess cyclohexylamine.

invention. relates to new oducts which are useful insecticides and synergists for pyrethrins- 1,: I v 1T1:-

PT; i

The products of the invention are prepared from chloromethyl or bromomethyl dihydrosafrol 5 and various amines, namely, primary and secondary alkylamines having from one to eight carbon CHTCHPCH; 15 The main product was distilled in vacuo at \o 174180 and 2 mm. It is an odorless, somewhat viscous oil, turning yellow on standing.

omx The product prepared as described was an effective insecticide and synerglst for pyrethrins.

Thus, when used with pyrethrins in the proportions of mg. of py ethrins and 300 mg. of the product in 100 ml. of odorless kerosene, the knockdown at the end of 10 minutes was 95.3% and the kill at the end of 24 hours was 43.1

26 on housefiies in the Poet-Grady test, whereas the O. T. I. (100 mg. of pyrethrins in100 ml. of odorless kerosene) gave a knockdown of 97.4% and a kill of 42.4 under the same. test conditions.

Example II The morpholine reaction product was prepared as follows: To 53 grams (0.265 mole) of chloromethyl dihydrosafrol dissolved in 50 ml. of henzene was slowly added with cooling a solution of 53 grams (0.61 mole) of morpholine dissolved in m1. of benzene. Th reaction commenced and a solid fraction separated, after-which the mixture was refluxed for four hours. The mixture was then cooled and washed with water to remove the hydrochloride salt of morpholine, and the solid fraction was thereafter separated and steamed to remove excess morpholine. The solid reaction product, after drying, analyzed 5.26% nitrogen calculated (4.84%).

The product prepared as described was an effective insecticide and synergist for pyrethrins.

CHIC} Thus, when used with pyrethrins in the proportions of 30 mg. of pyrethrins and 1000 mg. of the H CH, product in ml. of odorless kerosene, the

+ HNflflkymm 5o knockdown at the end of 10 minutes was 94% 0 and the kill at the end of 24 hours was 94% on housefiies in the Poet-Grady test, whereas the corresponding figures for the O. T. I. were 96% and 33%.

in which X is the chlorine or bromine atom, and they may be prepared in accordance with the teachings of my copending application, Serial No. 658,872, filed April 1, 1946, now- Patent 2,485,680, October 25, 1949, of which application the present application is a continuation-in-part.

Amines which may suitably be used in preparing the products of the present invention are methylamine, dlmethylamine, methyl ethyl amine, ethylamine, diethylamine, n-butylamine, di-n-butylamine, Z-ethylhexylamine, di-2-ethylhexylamine, etc.

The new products are suitably prepared by contacting the reactants when in solution in a low-boiling aromatic solvent, such as benzene, toluene or the xylenes, using at least about two moles of amine per mole of chloromethyl or bromomethyl dihydrosafrol and recovering the product by distilling it from the reaction mixture. For example, when a primary alkylamine and chloromethyl dihydrosafrol are used as reactants, the reaction may be illustrated by the following 40 equation:

om-nn-alk l The following examples illustrate the prepara- 3 Example III The dibutylamine reaction product was pre- I pared as follows: 68 grams (0.53 mole) of dibutylamine was dissolved in 23 grams of benzene, 53 grams (0.265 mole) of chloromethyl dihydrosafrol was added during cooling, the mixture was allowed to stand for one hour and was then refluxed for four hours- Waterwas then added, the oil was separated, the benzene distilled off then steam passed through the remainder to mess, turning s htly yell w on standing. I y

remove excess dibutylamine; The,,-main product distills in vacuo at 171-174 and 3.7 mm. it is an 4 I I claim:

1. The compounds of the generic formula /,0 CH:OH2CH3 H10 C Ha-A in which A is an' N-linkedz-radical selected from the group consisting of monoalkylamino and dialkylamino radicals having from one to eight carbon-atomsin each alkyl radical, cyclohexylamino radicals, morpholinyl radicals and piperidyl radi- I cals.

For example, they may be employed in solution in kerosene, as has been described, or they may be used as an active ingredient of insecticidal dusts.'

Thus, a suitable dust may be prepared by incorporating2.5% "of the product'and 0.2% of p'yrethrins into a carrier such as exhaustedpyrethrum flowers, and thereafter-diluting the carrier with three or four parts of talc,

The products of this inuentionmay Ice em ployed alone or as synergists for pyrethrins in the conventional types of commercial insecticides:

he compou ds of claim 1 in which A is a d alkylamino radical.

3. The compounds of claim 1 in which A is a dim-:butylamino radical.

4. The compounds of claim 1 in which A is a cyclohexylamino radical.

5. The compounds of claim 1 in which A is a morpholinyl radical. nE MANWAens.

No references cited. V 

1. THE COMPOUNDS OF THE GENERIC FORMULA 